Composition containing resinous type products



Patented May 16, 1944v COMPOSITION CONTAINING TYPE PRODUCTS nrsmoos Rudolph R. Grant, Los Angeles, Calif., assignor oi' one-fourth to Max Isaacson, Dayton, Ohio, and S01 Shappirio, Washington, D. C.

No Drawing, Application April 5, 1940, Serial No. 328,149

28 Claims. (01. 106-8) rather complex, and in view of the dependence ofv the resinification on the presence of relatively expensive components, the cost of such products has militated against their use in a number of Among the objects of the present invention is the production of resin type reaction. products from glyceride oil components including the glyceride oils and the acids thereof converted into such resin type products by economical methods.

Other objects include modification of such resinous type complexes by the inclusion of components which materially aflect the properties and condition them for utilization in various directions.

Still further objects and advantages of the present invention will appear from the more detailed description given below, it being understood, however, that this more detailed description is given by way of explanation and illustra tion only, and not by way or limitation, since various changes therein may be made by those skilled in the art without departing from the spirit and scope of the present invention.-

In accordance with the present invention, the glyceride oils, or the acids from such glyceride oils, either individually or in admixture, are heat treated in the presence ofan oxide of an alkaline earth metal, or an oxide of magnesium, until the desired reaction product is, obtained. Elevated temperatures are required in producing such re-' action products.

The glyceridefoils that may be employed in clude both animal' and vegetableoils, or from ployed in producing these condensation products.

It will be understood that each and every oil does not give identically the same type of reaction products, but the reaction products obtained from these various oils fall into the general classes of resin-type reaction products, the characteristics of which may be modified over a wide range, as more particularly pointed out below, to give products which are resins, gums, balsams, or pitches, etc. As illustrative of the various oils that may be employed, the various animal, fish and vegetable oils may be utilized, and particular attention may be called to the following oils: almond, cashew, castor, cocoanut, corn, cottonseed, fish liver oils, hemp, linseed, maize, menhaden, mustard, neats-Ioot, oiticica,.olive, palm, peanut, perilla, poppy, rape, soya bean, sperm, sunflower, tung, whale, and wood oils, as well as the fatty acids derived therefrom. The fatty acids that may' be employed are particularly those having more than 12 carbon atoms, including both saturated and unsaturated acids, and as exemplary of the acids there may be mentioned stearic, palmitic, caproic, caprylio, capric, lauric, oleic, linoleic, linolenic, ricinoleic, eleostearic, isolinolenic, myristic, arachidic, erucic, hypogeic. Mixtures of these acids with each other or mixtures of the acids with the oils, which oils may be either the same or difl'erent from those from which the acids are derived, may be employed, any combination desired being utilizable, and the properties or the resulting complexes necessarily varying.

The complex mixtures of acids derived by saponiflcation from the oils are excellent materials for utilization, and

' rancid oils containing both the oils and substantial quantities of acid may be employed. The oils or oil acids may be blown, boiled or otherwise treated as indlcated above. v

0f the metallic oxides employed'in producing these reaction products, magnesia or magnesium I oxide gives unique type reaction products, and of better character than that obtained from the oxides of the alkaline earth metals. Theoxides employed in the process should be substantially free from moisture, and where suchoxides, such I as those of magnesium and calcium are emanother point oi view or classification, the drying,

ployed, they should be substantially free from carbonates, and where such oxides are produced by calcination of natural products lik mag nesite. or lime stone, etc, the products should for best results be substantially calcined 'to' remove the presence of carbonates and carbon dioxide: Substantial amounts of the oxides are utilized in producing the reaction products in ac-'.

cordance with the present invention, but it has been round that variation in the amount of oxideing substantial amounts of the oxides, results in the production of balsam-type products. Still further reduction in the amount of oxides, but still employing substantial amounts of such oxides, results in the production of pitch-like products. In carrying out the reactions, the oxides of whatever character employed, are desirably thoroughly intermixed with the oil before the heat treatment, and certainly before the final stages of the heat treatment, so that the reaction will proceed vigorously and thoroughly throughout the reaction mass.

The heavy oxide of magnesium, substantially free from carbonates, has given the best results in producing these reaction products, although calcium oxide and mixtures of calcium and magnesium oxide, such as in equal parts, may also be utilized, although a noted, the oxide should be substantially free from moisture or carbonic acid and its compounds. The best types of resinous products are obtained when carbonic acid or its derivatives are absent, and such derivatives appear to retard the process and prevent the full resin reaction. Where balsams, for example, are produced, a good calcined lime of the commercial type can be used, and particularly where such commercial product is a mixture of the oxides of calcium and magnesium, but will not make as hard a resin generally speaking as magnesia alone.

In the production of products where color is 4 not a militating influence, the oxide employed may desirably be dolomitic, since dolomitic limes contain substantial amounts of magnesia. For example, dolomitic limes containing and upwards of magnesia, and running as high as 30, 35 and 40% magnesia ofier a cheap source of magnesium oxide for the production of products in accordance with the present invention.

Where such dolomitic oxides are employed, desirably they areutilized in a. thoroughly ground condition, and preferably are calcined immediately prior to their utilization, or if already obtained in a calcined condition, may be subjected to recalcination.

tion is suflicient to give the desired reaction product. While the reaction may be carried out in open vessels, exclusion or air will generally give lighter colored products; but it will'be apparent that when the vigorous, spontaneous and exothermic reaction begins, dense clouds of gases and vapors are evolved which tend to sweep out any oxygen from the reaction vessel. Rapid heating up to this point of exothermic reaction is desirable, although the oils exhibit different capacities for absorption of heat, and with an oil like castor oil, the application of heat is somewhat slower than with the other oils.. In those cases where there is any tendency to flashing, as in connection with linseed oil during the heatingup stage, a loose cover may be applied over the heating vessel to keep the air out as far as possible. The reaction is so vigorous that when open vessels ar employed, it is desirable to have the heating chamber of'a capacity about fourv times the quantity of a mixture being treated, so that the oil mixture will not be carried out of the heating chamber. Where the gases and vapors from the reaction vessel are permitted to escape into the air, it is desirable first to treat them with water, as by means of a water spray to absorb most of th odor, then permitting the gases and vapors to pass to the atmosphere. The water spray if of low enough temperature will condense, condensible matter from the gases and vapors, or a condenser may be employed for that purpose. In producing the resinous type condensation products or polymerization products, an excess of oxide is not disadvantageous, since any oxide apparent in the material may be readily removed therefrom while the resin is in the fluid stage. It has also been found desirable to permit the reaction to proceed in the presence of reaction products produced in a previous run, and the residues of reaction products that remain in the reaction vessel may be employed for that purpose.

To some extent, the amount or quantity of oxide employed will vary with variations in the grade of oil employed.

The following specific examples will illustrate the production of reaction products in accordance with the present invention.

A castor oil resin may be prepared as follows.

Approximately 1 lb. of magnesium oxide is used to 14 lbs. of oil. The castor'oil reaction beginl at temperatures of approximately 510 to 520 1'. Th mixtur of oil and oxide, utilizing mathesium oxide particularly for thi purpose, is heated rapidly until a temperature of about 520' F. is obtained. The external heat is then cut 0!! as reaction gas begins to be emitted, and the reac;

The mixture of desired ingredients is heat tion is permitted to proceed under it own heat.

treated to produce the reaction products, and in such heat treatments, the most desirable method has been found to involve heating the mixture of desired ingredients quite rapidly until gas in substantial amount is evolved. At this point, external heating is discontinued, and the reaction permitted to proceed spontaneously and exothermically, which it does quite vigorously giving of! large volumes or dense clouds of gas. usually of obnoxious character, some, instances are infiammable. At the start of the spontaneous or exothermic reaction, a change in character and'odor of 'gas given oi! may be noted. Usually reaction for from 5 to 10 minutes during the exothermic stage and which in variation in properties of .the complex with variations in proportions of oxide with variations in the ratio of lime to magnesia present. The higher ratios of magnesia to lime in oxide Droof reac- 7 duce the hardest products with given proportions ofoil to oxide, and decrease in the ratio of grains of oxide to tung oil reaction in the may reach a temperature of 690 magnesia to lime present result in a softening of the product down to balsam-type materials. Thus with blown castor oil and a dolomitic oxide containing about 36% of magnesia, using 100 1 ounce of oil, there was obtained a light, brownish'resin, quite brittle and relatively hard. With 60 grains of such oxide to the ounce of oil; a tougher, somewhat darker product is obtained. With 40 grains of oxide, desirably well calcined before use, a darker brown resin is obtained, substantially tougher than that of the preceding products, but still brittle enough to fracture. With 30 grains of such dolomitic oxide containing about 35 to 40%,

. magnesia, the product obtained was a gummy material fairly soft and workable under moderate pressures, the product being approximately the same in color as that of the preceding sample. Thus the dolomitic oxides ofier an inexpensive source of magnesia which enables products to be produced which in cost adapt them to utilization in asphaltic type mixtures, enamels and emulsions, and for waterproofing mixtures where cost is a desideratum.

Similarly a tung oil reaction product may be utilized using the same proportions as that given above for magnesium oxide, namely about 1 lb. of magnesium oxide to 14 lbs. of tung oil. The exothermic stage usually proceeds,between; temperatures of about 530 to 560 F. The mass is heated up rapidly until the reaction takes place, which will generally be evidenced at about 540, and then permitted to proceed exothermically as indicated above. More care isrequired in handling tung oil than in some of the other oils, and while rapid heating is best,'the heat cannot be applied as fast as in the case of castor oil. i

It is noteworthy that the tune oil does not gelatinlze during this treatment. The tung oil product is a quite brittle resin, easily powdered or ground, having a color and appearance quite similar to that of ordinary shellac.

III

A linseed oi1 resin may similarly be produced from linseed oil, together with the same proportion of magnesium oxide as that indicated above for castor oil. The reaction usually begins at about 560 F., and during the exothermic reaction after the external heat has been cut 011. F. In view of the tendency of the oil to flash, while rapid heating is employed, care should be utilized. The heating vessel may in this instance be covered to keep out air as far as possible. The linseed oil resin is a quite brittle, translucent, ready to grind product.

The following examples particularly illustrate the use of the edible oils in the production of resins. IV

A resin may be roduced from soya bean oil, handling the .oil in much the same manner as that described above for castor oil. The reaction temperature for exothermicreaction begins about 540 F., and the oil and oxide mixture is heated up rapidly to that temperature, after which the heat may be discontinued to permit the reaction to p oceed exothermically. The. resin obtained is somewhat softer than that produced with the linseed and tung oil referred to above, but is still quite brittle, almosttranspab ent, and of a clear brownish yellow color.

Corn oil may be utilized in producing a resin, handling the corn oil in substantially the same way as that set forth above for the castor 0r soya bean products. The mixture with magnesium oxide in the proportions indicated, is heated rapidlyto a temperature of about 600 F. after which the external heat is discontinued, and the reaction permitted to proceed exothermically. A

substantially straw colored product, tending. to opaqueness and more gum-lik in character is obtained with the corn oil, although the resin is still quite brittle and easily frangible.

The following example illustrates the utilization of fatty acids themselvesin the production of resins in accordance with the present invention.

and in mixed solvents as, for example, a mixture of equal parts of alcohol, benzol and carbon tetrachloride. Turpentine will dissolve many of them, and this is true of other solvents like acetone and toluol. Solubility may be controlled by the components utilized in producing the reactioncomplexes, so that products soluble in kerosene or gasoline, or other selected solvents, may thus be produced.

The synthetic resins produced by the present invention have a tendency to bleach'out when exposed to sunlight, andthis is particularly true of the ricinoleic acid resin described above.

The various properties of these resins make them utilizable widely in lieu of synthetic and natural resins generally in the industries in the production of coating compositions, molding compositions, etc. These resins possess insulating properties, and may desirably be employed, therefore, in the production of articles used in electrical apparatus or systems, either employing ing compositions to produce I molded articles,

with fillers, desirable articles may varnish. A varnish of castor or tung resins yields a floor filler of wax-like finish, that appears -to improve with washing.

Generally the r sins produced in accordance with the present in yention are harder thanmatural resins and melt at natural and synthetic, for

- above by the utilization of glyceride oils and their with other types of resins may higher temperatures than the natural resins, which property further makes them desirably employed in electrical equipment and installations. Thus a resin of either castor oil, tung oil or linseed oil may be utilized with lower quantities of magnesium oxide to oil. For example, slightly more than one-half of the amount of magnesium oxide given in the castor oil example above, to produce tough, dense or flexible stages that can be applied to coils to seal punctures therein as in spark coils and transformers of the high tension type.

The resins may be utilized as binders in producing nonshatterablc glass, as for example, where two or more panes of glass are sandwiched together by means of a binder oi the synthetic resins disclosed herein, or composition of the cellulose esters, such as nitrocellulose, together with the resins, may be employed. The bleaching out characteristic of the ricinoleic acid resin, for example, is particularly valuable for such purposes.

The resins of the present invention desirably may be employed as plasticizers in cellulose ester compositions or lacquers, particularly of the cellulose nitrate or cellulose acetate type. And these resins may be employed as plasticizers with cellulose nitrate or cellulose acetate, or other cellulose esters and others in producing various types of products including, for example, the so cellulose acetate threads or yarns used in the production of fabrics and textiles.

These'resins may be used in lieu of other resins, the sizing of paper, in sizing compositions so and either by application to the finished paper, or incorporated into the heater in the usual resin formulations before the paper composition is sheeted.

In view of the insulating properties of the resins, they may be utilized in solutions for application to metallic conductors or wires to produce insulating coatings thereon, or for the impregnation of the usual type of cotton or other coatings on such wires, or the wires may be run through the molten resin to produce a coating thereon. Solutions of the resins may also be employed as primer coats on metallic and wood surfaces, and particularly as undercoats over which drying oil types of varnishes are to be applied. They may, however, also be employed as undercoats under lacquers 'of the nitrocellulose, etc. type.

Coatings of these resins may be baked to increase their hardness. I

The invention has been particularly illustrated fatty acids, but mixtures of the glyceride oils, or mixtures of the fatty acids, or mixtures of the oils and acids may be employed in producing these reaction products. While the incorpora- 1" tion of other substances, particularly of organic a character is not required in the production of these resins, the resins may be modified by the inclusion of other organic substances with the reaction mixture before the heat treatment is begun. o5

Mixtures of the resins of the present invention be employed for particular purposes, and among such resins that may be utilized there may be mentioned the phenol-formaldehyde types of resins. the phthalio' 7 glyceride types of resins, the vinyl resins, the urea-formaldehyde types of resins, etc. 1

The products producedin accordancewith the invention set forth above may include various additions, particularly introduced during the re- (5 resinlfication reaction. v sirably be employed to modify the resins for parized wood, soya bean molten condition makes I phaltic base characteristics.

; ing'components, such as types of products produced action itselt, which additions materially aflect the characteristics of the products obtained. Fillers, for example, may be utilized, mineral fillers, such as clays, diatomaceous earth, bentonite, asbestos, mica, ground glass, and the various heavy metal oxides may be employed, and such mineral fillers may be introduced into the reaction materials and incorporated therewith, and be present during the resin-forming treatment, under which conditions more uniform desirable products are obtained than from incorporation of filler subsequently alter the Organic fillersmay deticular purposes, including ground cork, pulverflour and the various vegetable fillers and fibers. Such organic materials should not be incorporated at any temperature where heat decomposition or destruction to an undesirable extent will occur. Consequently, the organic fillers are generally introduced after the resiniiication reaction at the higher temperatures has been carried out, and such fillers may be incorporated during the cooling down of the prodnot, or after it has reached room temperature. Incorporation of fillers while the product is in thorough dissemination more readily carried out.

More importantly various substances may be incorporated into the reaction mixture which very materially modify the characteristics or the resulting product enabling asphaltic type substances, waxy materials, rubbery products, etc. to be obtained. Such added components may generally be referred to as hydrocarbonaceous under which tars, including both coal tar and petroleum tar, pitches and the like, as well as mineral oils and their distillates, such as for example, lubricating oils, etc., both of paraffin, semi-asphaltic and as- The hydrocarbons,- ceous components added should desirably be of such character and volatility that they are retained in the reaction mass under the conditions of treatment, and consequently the higher boilthe lubricating oils, are more desirably employed.

The iollowing examples will illustrate various by such modifications of the fundamental resin-forming reaction.

VII

Thus a mixture or equal parts of a par'aflln base lubricating oil and raw castor oil was heated with a dolomitic oxide containing about 30 percent of magnesium oxide, in the proportions of 50 grains of oxide per ounce of oil mixture. '-The reaction took place at about 550 F, and a waxlike resin was obtained which could be readily crumbled between the fingers.

the reaction mixture ena le control or the properties to be obtained as desired. Variations in the proportions of lubricating oil to vegetable oil materially affects the resulting properties. The lubricating oil would give no substantial reaction product with the oxide under the conditions of heat treatment in the absence of the vegetable 011, whereas the characteristics of the products obtained from the vegetable oil in the presence of themineral oil components are markedly di!-' ferentiated from those of the straight vegetable oil resins.

.The production of synthetic waxes or wax-like products in accordance with the present inventhose which result term are included the bitumens,

Such product and I the incorporation of mineral oil components into as tung, linseed, soya bean, as indicated herein may be employed, either with tion is of great importance enabling products of controlled characteristics suitable for a variety of P poses to be produced, the characteristics of which can be modified for particular products and utilities.

Thus metal polishing wax-like materials may be readily produced of unique characteristics. The reaction of a mixture of equal parts of raw castor oil and mineral oil, using 50 grains of magnesium oxide to the ounce of oil mixture reacted at a temperature around 600 gives a relatively soft, semi-fluid mass, excellently adapted for such metal polishing compositions, etc., used alone or in admixture with other desirable components.

, Similarly wax-like materials may be produced utilizing paraflin in varying proportions. Thus raw castor oil and commercial paraflln wax may be reacted together with magnesium oxide, using 50 grains of oxide per ounce of the named materials, the ratio of paraflln wax to raw castor oil being, for example, from 30 to 50% of the oil to 70-50% in accordance with the present invention. More or less soft, waxy materials are thus produced whose properties vary with the ratio and charactor of components employed, the higher proportions of paraflln wax giving resulting products more waxy in character. Products produced with the proportions indicated are relatively soft masses of distinct waxy feel and fracture. While.

castor oil and paraflin wax have been referred to in producing wax-like products, other oils such etc., or their acids the mineral waxes such as paraflin, etc. or with the animal and vegetable waxes, such as beeswax, carnauba, candelilla, montan, etc.

A mixture of one-fourth paraflin wax with three-fourths light blown castor oil reacted at temperatures of about 530 with magnesium oxide in the ratio of 50 grains of oxide per ounce. of oil and wax mixture gives a brown wax-like product that is quite pliable but exhibits pronounced wax characteristics.

Development of these synthetic waxes whose properties may be. readily-controlled with respect to solubility, meltingpoint, etc. is of great a technical significance. The products produced with natural waxes incorporated into the re-' action mass. generally products :of substantially: higher melting point than the natural products themselves, and which products all have high insulating value.

. I I Illustrating the productionof an asphaltic type product, fish oil was admixed "with petroleum byproduct tar in the ratio of 40% fish oil to 60% tar, and the product reacted with calcined dolo mitic lime containing about 30% magnesia in the ratio of 100 grains of lime per ounce'of oil.

of the paraffin wax, heated and reacted In making such wax-like products any of the higher boiling mineral components ma be employed, since waxgive resulting 'wax-like The reaction proceeded at about 600 F., the resulting product when cooled beinga tough,

tenacious, gummy material. v Similarly a plastic tar-like material can be 5 obtained by reacting linseed oil and petroleum tar in equal amounts with a dolomitic oxide, the reaction proceeding at 560 F., the product being I a dark, fairly brittle asphaltic-like material, useful in a wide variety of ways, the utilities illustratingall of these tar-like or asphaltic type reaction products. production of linoleums, and ofi'er great advantages over the more expensive boiled oil, linoleum bases.

Another example of a tar type product is illustrated by the reaction of a mixture of 437 parts of a commonly used roof tar mix with 70 parts fish oil, and 100 parts of lime and magnesium oxide heated to about 500. The resulting product is quite dark and tough, although frangible.

While the original standard roof tarmix employed was relatively soft at room temperature and very tough, its properties are very materially modified as indicated above by treatment in accordance with the present invention.

Products produced in accordance with the present invention may be blended with rubber, and particularly by utilizing the lighter colored products produced herein, such as the castor resins, various proportions may be employed, and they may be incorporated on mixing rolls or by the use of a solvent, such as benzol. A product obtained by blending equal parts of plantation rubber arid castor resin, the latter produced from castor oil using 30 grains of magnesium oxide per ounce of oil, blended with benzol, on evapo-' ration of the solvent gave a highly elastic, light colored rubber material exhibiting marked tensile strength.

40 If only small percentages of the vegetable or animal oil is employed with the tar-like products,-

such as petroleum by-product tar, the conditions of reaction otherwise being like those in Example 8 above, material suitable for use in roofing is obtained. An advantage of such products for roofing purposes produced in accordance with the present invention is their greater resistance to water and heat. While many commercial asphalt mixes are made by additions of resins,

such as rosin or glyceride oils or fats, their re-' sistance to weathering is not as great as necessary, particularly under certain atmospheric conditions. The improved waterproof characteristics of products produced in accordance with the present. invention solve those problems in the art.

The products of various types produced in accordance with the present invention due to their insulating properties may be used in the proture, shellac. as insulations for electric cords and wire, and for a variety of other purposes as in theimpregnation of textile materials, asbestos, etc., for brake band use. For some of these purposes, the dark, tar-like reaction products may be employed, and it is noteworthy that even a product containing as low as 10% fish oil, as indicated above, which is extremely soft and plastic, gives unique properties to tars, pitches etc. produced.

While elevated temperatures have generally been indicated abovein the'production of these complexes, the actual temperature employed necessarily depends on the particular materials undergoing treatment. With most of the glyc- They may be utilized in the duction of insulating tapes and cloths, as armaproduced and the under the conditions of exothermic heat reaction product of a component of true. resinous character eride oils and their acids marked reaction begins at about 500 F., and in some instances as low as 450 F. The upper range of temperature necessarily varies with the character of product added components. With glyceride oil materials, the temperature seldom rises about 700 F., but for incorporation of the petroleum'type materials, particularly heavier oils and waxes, higher temperatures'may be employed as, .for example, temperatures in the range of 800 to 900 F.

Having thus set forth my invention, I claim:

1. A composition containing-a non-gaseous hydrocarbonaceous component and an exothermic heat reaction product of true resinous character from a component selected from the group of glyceride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides.

2. A composition containing a tar and an exothermic heat reaction product of true resinous character from a component selected from the group of glyceride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides.

3. A wax-like polishing composition containing a petroleum oil component of such character and volatility as is retained in the reaction mass treatment and a resinous selected from the group of glyceride oils and the acids derived therefrom, and an oxideselected from the group consisting of the alkaline earth metal and magnesium oxides.

4. A composition containing a hydrocarbonaceous component-selected from the group consisting of petroleum oil and parafiin wax and an exothermic heat reaction wax-like component I produced with a glyceride oil and magnesium oxide. a

5. A composition containing a lubricating oil and a resinous exothermic heat reaction product of a. component selected from the group of glyc eride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and magnesium-oxides. 6. A composition containing a bituminous component and an exothermic heat reaction product from a component selected from the group of glyceride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides.

'7. A composition containing anon-gaseous hydrocarbonaceous component and an exothermic heat reaction product of true resinous character from glyceride oil acids, an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides.

8. A composition containing a non-gaseous hydrocarbonaceous component and an exothermic heat reaction product of true resinous character from a glyceride oil, an oxide selected from the group consisting of the alkaline earth metal I and magnesium oxides.

9. A composition-containing a non-gaseous hydrocarbonaceous component and an exothermic heat reaction product'of true resinous character from a component selected from the group of non-drying glyceride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and ma nesium oxides.

.of alkaline earth metal and magnesium 10. A composition containing a non-gaseoushydrocarbonaceous' component and an exothermic heat reaction product of true resinous character from. a component selected irom the group of semi-drying glyceride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides.

11. A composition containing a non-gaseous hydrocarbonaceous component and an exothermic heat reaction product of true resinous character from a component selected from the group of drying glyceride oils and the acids derived therefrom, and an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides.

12. A composition containing an exothermic heat reaction product of true resinous character from a component selected from the group of glyceride oils and the acids derived therefrom, and an oxide selected from the group consistin of alkaline earth metal and magnesium oxides, and a mineral filler.

13. A composition containing an exothermic heat reaction product of true resinous character from a component selectedfrom the group of glyceride oils'and the acids derived therefrom, and an oxide selected from the group consisting oiddes,

and an organic fllle'r.

14. A composition containing a resinous reaction product of a component selected from the group of glyceride oils and the acids derived therefrom and an oxide selected from the group consisting of alkaline earth metal and magnesium oxides and rubber.

15. The method of making resinous reaction products which comprises heating a component selected from thr group of glyceride oils and the acids derived therefrom and an oxide selected from the group consisting of alkaline earth metal and magnesium oxides in the presence of a nongaseous hydrocarbonaceous component at elevated temperatures until a reaction product of resin type character is obtained.

16. The method of producing resinous reaction products which comprises heating glycerid oil acids in the presence of an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides at elevated temperatures until gas in substantial amount is given 01!, and then permitting the reaction to continue exothermically until a reaction product of resin type character is obtained.

17. The method of producing compositions containing resinous reaction products which comprises heating a component selected from the group of glyceride oils, and the acids derived therefrom with an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides at elevatedtemperatures in the presence of aflfllleruntil gas in substantial amount is given 0 1 18. The method of producing compositions containing resinous reaction products which comprises heat treatin a component selected from the group of glyceride oils and the acids derived therefrom in the presence of an oxide selected from the group consisting of alkaline earth metal and magnesium oxides at elevated temperatures until gas in substantial amount is given off, and incorporating the reaction product with an organic filler.

earth metal and magnesium oxides.

21. A composition the group of non-drying glyceride oils and the acids derived therefrom,'and an oxide selected from the group consisting of the alkaline earth metal and magnesium oxides] 23. A composition containing paraflin wax and metal and magnesium oxides. I 24. A composition containing parafiin wax and an exothermic heat reaction product of true resinous character fr in a component selected from the acids derived an oxide selected from the group metal and magtherefrom, and consisting of the alkaline earth nesium oxides.

the group consisting of the alkaline earth metal and magnesium oxides.

27. A composition containing a wax and anexothermic heat reaction product of true resinous character from a glyceride oil, and an oxide sestituting from to ponents collectively.

28. A composition containing a non-gaseous hydrocarbonac'eous component and an exothermic RUDOLPH R. GRANT. 

